Thiol dyes

ABSTRACT

Disclosed are thiol dyes of formula (1), wherein R 1  is hydrogen; C 1 -C 12 alkyl; or phenyl-C 1 -C 4 alkyl; X is C 1 -C 12 alkylene; C 2 -C 12 alkenylene; C 5 -C 10 cycloalkylene; C 5 -C 10 arylene; or C 5 -C 10 arylene-C 1 -C 10 alkylene; Y is the residue of an organic dye which corresponds to the formula (1 a ), wherein R 2  is hydrogen; or C 1 -C 5 alkyl; R 3  is a radical of formula (1 a   1 ): (1 a   2 ); or (1 a   3 ); or R 2  and R 3  together with the linking carbon atom C form a 6 to 10 membered carbocyclic ring which may optionally be a condensated aromatic system and may contain one or more than one hetero atom; and R 4 , R 5  and R 6  independently form each other are hydrogen, or C 1 -C 5 alkyl; Z is H; or a thio ester group of formula (1 b ), wherein A is O; S; or N—R9; B is —OR7; —NR7R8, or —SR7; and A is O; S; or N—R 9 ; B is —OR 7 ; —NR 7 R 8 , or —SR 7 ; and R 7 , R 8  and R 9 , independently from each other are hydrogen; C 1 -C 12 alkyl C 6 -C 12 aryl; or C 6 -C 12 aryl-C 1 -C 12 alkyl. The compounds are useful for the dyeing of organic materials, such as keratin fibers, preferably human hair.

The present invention relates to novel thiol dyes, compositions thereof,to processes for their preparation and to their use for the dyeing oforganic materials, such as keratin fibers, wool, leather, silk,cellulose or polyamides, especially keratin-containing fibers, cotton ornylon, and preferably hair, more preferably human hair.

It is known, for example, from WO 95/01772 that cationic dyes can beused for the dyeing of organic material, for example keratin, silk,cellulose or cellulose derivatives, and also synthetic fibers, forexample polyamides. Cationic dyes exhibit very brilliant shades. Adisadvantage is their unsatisfactory fastness to washing.

The technical problem is to provide dyes that are distinguished by deepdyeing having good fastness properties with respect to washing, light,shampooing and rubbing.

Accordingly, the present invention relates to compounds of formula

wherein

-   R₁ is hydrogen; C₁-C₁₂alkyl; or phenyl-C₁-C₄alkyl;-   X is C₁-C₁₂alkylene; C₂-C₁₂alkenylene; C₅-C₁₀cycloalkylene;    C₅-C₁₀arylene; or C₅-C₁₀arylene-C₁-C₁₀alkylene;-   Y is the residue of an organic dye which corresponds to the formula

wherein

-   R₂ is hydrogen; or C₁-C₅alkyl:-   R₃ is a radical of formula

or R₂ and R₃ together with the linking carbon atom ¹C form a 6 to 10membered carbocyclic ring which may optionally be a condensated aromaticsystem and may contain one or more than one hetero atom; and

-   R₄, R₅ and R₆ independently form each other are hydrogen, or    C₁-C₅alkyl;-   Z is H; or a thio ester group of formula

wherein

-   A is O; S; or N—R₉;-   B is —OR₇; —NR₇R₈; or —SR₇; and-   R₇, R₈ and R₉, independently from each other are hydrogen;    C₁-C₁₂alkyl; C₆-C₁₂aryl; or C₆-C₁₂aryl-C₁-C₁₂alkyl.

C₁-C₁₂alkyl is for example, methyl, ethyl, propyl, isopropyl, n-butyl,sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl,2,2′-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl,1,1′,3,3′-tetramethylbutyl or 2-ethylhexyl, nonyl, decyl.

C₁-C₁₂alkylene is for example methylene, ethylene, propylene,isopropylene, n-butylene, sec-butylene, tert-butylene, n-pentylene,2-pentylene, 3-pentylene or 2,2′-dimethylpropylene, n-hexylene,n-octylene, 1,1′,3,3′-tetramethylbutylene, 2-ethylhexylene, nonylene,decylene, undecylene or dodecylene.

Alkylene may be straight-chain, branched, or, from C₅alkyl upwards,monocyclic or polycyclic, and may be interrupted by hetero atoms, suchas such as O, S, —CO—, N, NH, NR₅₄, —OCO—, —CO(OR₄)—, —CONR₄—,—(R₅)NC(O)—; for example C₁-C₁₀alkylene may be a reissue such as:—CH₂CH₂—O—CH₂CH₂—O—CH₂CH₂—, —CH₂CH₂—O—CH₂CH₂—, —CH₂CH₂—O—CH₂—,—CH₂—O—CH₂—, —CH₂CH₂—CH₂CH₂—O—CH₂—CH₂—, —CH₂CH₂—CH(N(CH₃)₂)—CH₂—CH₂—,CH₂—NH₂—CH₂—CH₂, —CH₂CH₂—NH—CH₂CH₂—, —CH₂CH₂—NCH₃—CH₂CH₂—, —CO—CH₂—,—CH₂CO—, —CH₂CH₂—NHCO—CH₂CH₂—, —CH₂CH₂—CONH—CH₃—CH₂CH₂—,—CH₂CH₂—NCH₃CO—CH₂CH₂—, —CH₂CH₂—CONCH₃—CH₃—CH₂CH₂—, —CH₂—NHCO—CH₂CH₂—,or —CH₂CH₂—NHCO—CH₂—, —CH₂CH₂—CONH—CH₂— or —CH₂—CONH—CH₂CH₂—.

C₅-C₁₀cycloalkylene is for example cyclopentylene, cyclohexylene,cycloheptylene, cyclo-octylene, cyclononylene or cyclodecylene.

C₅-C₁₀arylene is for example phenylene or naphthylene.

Aryl-alkylene is for example C₅-C₁₀aryl-C₁-C₁₀alkylene.

Alkyl-arylene is for example C₁-C₁₀alkyl-C₅-C₁₀arylene.

Preferably, in the compounds of formula (1)

X is C₁-C₁₂alkylene; and more preferably

X is ethylene.

Preferably, in the compounds of formula (1)

Y is selected from the radicals of formulae

Preferably, in the compounds of formula (1)

Z is selected from the radicals of formulae

wherein

R₇ and R₈ are defined as in formula (1).

Most preferably, the present invention refers to compounds of formula

wherein

R₁, R₃, X and Z are defined as in formula (1).

examples of compounds of the present invention are represented in thetable 1 below:

TABLE 1 Exemplified compounds of the present invention

Compound of formula R₃ R₁ X Z  (3)

H CH₃ C₂H₅ —CH₂—CH₂— —(CO)H —(CO)CH₃ —(CO)C₆H₅  (4)

CH₃ —CH₂—CH₂— —(CO)H —(CO)CH₃  (5)

CH₃ —CH₂—CH₂— —(CO)H —(CO)CH₃  (6)

CH₃ —CH₂—CH₂— —(CO)H —(CO)CH₃  (7)

CH₃ —CH₂—CH₂— —(CO)H —(CO)CH₃  (8)

CH₃ —CH₂—CH₂— —(CO)H —(CO)CH₃  (9)

CH₃ —CH₂—CH₂— —(CS)H —(CS)CH₃ (10)

CH₃ —CH₂—CH₂— —(CS)H —(CS)CH₃ (11)

CH₃ —CH₂—CH₂— —(CS)H —(CS)CH₃ (12)

CH₃ —CH₂—CH₂— —(CS)H —(CS)CH₃ (13)

CH₃ —CH₂—CH₂— —(CS)H —(CS)CH₃ (14)

CH₃ —CH₂—CH₂— —(CS)H —(CS)CH₃ (15)

CH₃ —CH₂—CH₂— —(CO)N(CH₃)₂ (16)

CH₃ —CH₂—CH₂— —(CO)N(CH₃)₂ (17)

CH₃ —CH₂—CH₂— —(CO)N(CH₃)₂ (18)

CH₃ —CH₂—CH₂— —(CO)N(CH₃)₂ (19)

CH₃ —CH₂—CH₂— —(CO)N(CH₃)₂ (20)

CH₃ —CH₂—CH₂— —(CO)N(CH₃)₂ (21)

CH₃ —CH₂—CH₂— —(CS)N(CH₃)₂ (22)

CH₃ —CH₂—CH₂— —(CS)N(CH₃)₂ (23)

CH₃ —CH₂—CH₂— —(CS)N(CH₃)₂ (24)

CH₃ —CH₂—CH₂— —(CS)N(CH₃)₂ (25)

CH₃ —CH₂—CH₂— —(CS)N(CH₃)₂ (26)

CH₃ —CH₂—CH₂— —(CS)N(CH₃)₂ (27)

CH₃ —CH₂—CH₂— —(CO)N(CH₃)₂ (28)

CH₃ —CH₂—CH₂— —(CO)N(CH₃)₂ (29)

CH₃ —CH₂—CH₂— —(CO)N(CH₃)₂ (30)

CH₃ —CH₂—CH₂— —(CO)N(CH₃)₂ (31)

CH₃ —CH₂—CH₂— —(CO)N(CH₃)₂ (32)

CH₃ —CH₂—CH₂— —(CO)N(CH₃)₂ (33)

CH₃ —CH₂—CH₂—

(34)

CH₃ —CH₂—CH₂—

(35)

CH₃ —CH₂—CH₂—

(36)

CH₃ —CH₂—CH₂—

(37)

CH₃ —CH₂—CH₂—

(38)

CH₃ —CH₂—CH₂—

(39)

CH₃ —CH₂—CH₂— *—C≡N (40)

CH₃ —CH₂—CH₂— *—C≡N (41)

CH₃ —CH₂—CH₂— *—C≡N (42)

CH₃ —CH₂—CH₂— *—C≡N (43)

CH₃ —CH₂—CH₂— *—C≡N (44)

CH₃ —CH₂—CH₂— *—C≡N (45)

CH₃ —CH₂—CH₂— —(CO)O—C₂H₅ (46)

CH₃ —CH₂—CH₂— —(CO)O—CH₃ (47)

CH₃ —CH₂—CH₂— —(CO)O—CH₃ (48)

CH₃ —CH₂—CH₂— —(CO)O—CH₃ (49)

CH₃ —CH₂—CH₂— —(CO)O—CH₃ (50)

CH₃ —CH₂—CH₂— —(CO)O—CH₃ (51)

CH₃ —CH₂—CH₂— —(CS)O—CH₃ (52)

CH₃ —CH₂—CH₂— —(CS)O—CH₃ (53)

CH₃ —CH₂—CH₂— —(CS)O—CH₃ (54)

CH₃ —CH₂—CH₂— —(CS)O—CH₃ (55)

CH₃ —CH₂—CH₂— —(CS)O—CH₃ (56)

CH₃ —CH₂—CH₂— —(CS)O—CH₃ (57)

CH₃ —CH₂—CH₂— —(CS)S—C₂H₅ (58)

CH₃ —CH₂—CH₂— —(CS)S—CH₃ (59)

CH₃ —CH₂—CH₂— —(CS)S—CH₃ (60)

CH₃ —CH₂—CH₂— —(CS)S—CH₃ (61)

CH₃ —CH₂—CH₂— —(CS)S—CH₃ (62)

CH₃ —CH₂—CH₂— —(CS)S—CH₃

A further enbodiment of the present invention relates to processes forthe preparation of the dyes of formula (1).

Generally, the process comprises condensating the methylenic compoundR₃H and/or R₂H with the amino benzophenone compound of formula (1c) tothe compound of formula (1d) and subsequently-reacting this compound togive the compound of formula (2) according to the following reactionscheme:

wherein

R₃ is radical of formula

and R₂ is simultaneously hydrogen; or

-   R₂ and R₃ together with the linked carbon atom ¹C of formula (2)    form a condensed carbocyclic ring of formula

-   Hal is a halogen atom; and-   R₁, X and Z are defined as in formula (1).

The reaction is generally initiated by contacting, for example by mixingtogether the starting compounds or by dropwise addition of one startingcompound to the other.

Customary, the temperature is in the range of 250 to 400 K, preferablyin the range of 270 to 300 K during the mixing of the startingcompounds.

The reaction time is generally dependent on the reactivity of thestarting compounds, on the selected reaction temperature and on thedesired conversion. The reaction time is usually in the range from 3hours to 3 days.

The selected reaction pressure is generally in the range from 50 kPa to3 MPa, especially from 100 kPa to 1 MPa, and is more especiallyatmospheric pressure.

Preferably the reaction is carried out in the presence of a catalyst.

The molar ratio of compound of formula (1b) to the catalyst is generallyselected in the range from 10:1 to 1:5, especially in the range from10:1 to 1:1.

Preferred are basic catalysts as tertiary amines or acid catalysts, HAand Lewis acids like Ag⁺.

In addition, the reaction may be carried out with or without a solvent,but is preferably carried out in the presence of a solvent, preferablyorganic solvents or solvent mixtures.

Preferred solvents are alcohols like methanol, ethanol, propanol,2-propanol or butanol; nitriles like acetonitril or propionitril; amideslike dimethylformamide, dimethylacetamide or N-methylpyrolidone;halogenated hydrocarbons like chloroform, methylenechloride,trichloro-ethylene or chlorobenzene; or other solvents likedimethylsulfoxide or water or mixtures of the mentioned solvents.

The product prepared according to the process of the present inventionmay advantageously be worked up and isolated, and if desired bepurified.

Customary, the work up starts by decreasing the temperature of thereaction mixture in the range from 350 to 273 K, especially in the rangefrom 320 to 273 K.

It may be advantageous to decrease the temperature slowly over a periodof several hours.

In general, the reaction product is filtered off and then andsubsequently dried.

Filtration is normally carried out in standard filtering equipment, forexample Büchner funnels, filter presses, pressurised suction filters,preferably in vacuo.

The temperature for the drying is dependent on the pressure applied.Drying is usually carried out in vacuo at 50-200 mbar.

The drying is usually carried out at a temperature in the range from 313to 363 K, especially from 323 to 353 K, and more especially in the rangefrom 328 to 348 K.

Advantageously the product is purified by recrystallisation afterisolation.

The dyes according to the invention are suitable for dyeing organicmaterials, such as keratin-containing fibers, wool, leather, silk,cellulose or polyamides, cotton or nylon, and preferably human hair. Thedyeings obtained are distinguished by their depth of shade and theirgood fastness properties for example to washing, fastness to light,shampooing and rubbing. The stabilities, in particular the storagestability of the dyes and the dyes in formulations according to theinvention are excellent.

Generally, hair dyeing agents on a synthetic base may be classified intothree groups:

-   -   temporary dyeing agents    -   semipermanent dyeing agents, and    -   permanent dyeing agents.

The multiplicity of shades of the dyes can be increased by combinationwith other dyes.

Therefore the dyes of formula (1) of the present invention may becombined with dyes of the same or other classes of dyes, especially withdirect dyes, oxidation dyes; dye precursor combinations of a couplercompound as well as a diazotized compound, or a capped diazotizedcompound; and/or cationic reactive dyes.

Direct dyes are of natural origin or may be prepared synthetically. Theyare uncharged, cationic or anionic, such as acid dyes.

The dyes of formula (1) may be used in combination with at least onesingle direct dye different from the dyes of formula (1).

Direct dyes do not require any addition of an oxidizing agent to developtheir dyeing effect. Accordingly the dyeing results are less permanentthan those obtained with permanent dyeing compositions. Direct dyes aretherefore preferably used for semipermanent hair dyeings.

Examples of direct dyes are described in “Dermatology”, edited by Ch.Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986,Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, p. 248-250, andin “Europäisches Inventar der Kosmetikrohstoffe”, 1996, published by TheEuropean Commission, obtainable in diskette form from the Bundesver-bandder deutschen Industrie-und Handelsunternehmen für Arzneimittel,Reformwaren und Körperpflegemittel e.V., Mannheim.

More preferred direct dyes which are useful for the combination with atleast one single dye of formula (1), especially for semi permanentdyeing, are: 2-amino-3-nitrophenol, 2-amino-4-hydroxyethylamino-anisolesulfate, 2-amino-6-chloro-4-nitrophenol,2-chloro-5-nitro-N-hydroxyethylene-p-phenylendiamine,2-hydroxyethyl-picramic acid,2,6-diamino-3-((pyridine-3-yl)-azo)pyridine,2-nitro-5-glyceryl-methylaniline, 3-methylamino-4-nitro-phenoxyethanol,4-amino-2-nitrodiphenyleneamine-2′-carboxilic acid,6-nitro-1,2,3,4,-tetrahydroquinoxaline,4-N-ethyl-1,4-bis(2′-hydroxyethylamino-2-nitrobenzene hydrochloride,1-methyl-3-nitro-4-(2′-hydroxyethyl)-aminobenzene,3-nitro-p-hydroxyethyl-aminophenol, 4-amino-3-nitrophenol,4-hydroxypropylamine-3-nitrophenol, hydroxyanthrylaminopropylmethylmorpohlino methosulfate, 4-nitrophenyl-aminoethylurea,6-nitro-p-toluidine, Acid Blue 62, Acid Blue 9, Acid Red 35, Acid Red 87(Eosin), Acid Violet 43, Acid Yellow 1, Basic Blue 3, Basic Blue 6,Basic Blue 7, Basic Blue 9, Basic Blue 12, Basic Blue 26, Basic Blue 99,Basic Brown 16, Basic Brown 17, Basic Red 2, Basic Red 22, Basic Red 76,Basic Violet 14, Basic Yellow 57, Basic Yellow 9, Disperse Blue 3,Disperse Orange 3, Disperse Red 17, Disperse Violet 1, Disperse Violet4, Disperse Black 9, Fast Green FCF, HC Blue 2, HC Blue 7, HC Blue 8, HCBlue 12, HC Orange 1, HC Orange 2, HC Red 1, HC Red 10-11, HC Red 13, HCRed 16, HC Red 3, HC Red BN, HC Red 7, HC Violet 1, HC Violet 2, HCYellow 2, HC Yellow 5, HC Yellow 5, HC Yellow 6, HC Yellow 7, HC Yellow9, HC Yellow 12, HC Red 8, hydroxyethyl-2-nitro-p-toluidine,N,N-Bis-(2-Hydroxyethyl)-2-nitro-p-phenylendiamine, HC Violet BS,Picramic Acid, Solvent Green 7.

Furthermore, the dyes of formula (1) may be combined with at least onecationic azo dye, for example the compounds disclosed in GB-A-2 319 776as well as the oxazine dyes described in DE-A-299 12 327 and mixturesthereof with the other direct dyes mentioned therein, and even morepreferred with cationic dyes such as Basic Yellow 87, Basic Orange 31 orBasic Red 51, or with cationic dyes as described in WO 01/66646,especially example 4, or with cationic dyes as described in WO 02/31056,especially example 6 (compound of formula 106); or the cationic dye offormula (3) as described in EP-A-714,954, or with a yellow cationic dyeof formula

wherein

-   R₁ and R₂ are each independently of the other a C₁-C₈alkyl; or an    unsubstituted or substituted benzyl;-   R₃ is hydrogen; C₁-C₈alkyl; C₁-C₈alkoxy; cyanide; or halide;    preferably hydrogen; and-   X⁻ is an anion; and preferably a compound of formula (DD1), wherein-   R₁ is methyl; R₂ is benzyl; R₃ is hydrogen; and X⁻ is an anion; or    wherein-   R₁ is benzyl; R₂ is benzyl; R₃ is hydrogen; and X⁻ is an anion; or    wherein-   R₁ is benzyl; R₂ is methyl; R₃ is hydrogen; and X⁻ is an anion.

Furthermore, cationic nitroaniline and anthraquinone dyes are useful fora combination with a dye of formula (1), for example the dyes asdescribed in the following patent specifications: U.S. Pat. No.5,298,029, especially in col 2, I. 33 to col 5, I. 38; U.S. Pat. No.5,360,930, especially in col 2, I. 38 to col 5, I. 49; U.S. Pat. No.5,169,403, especially in col 2, I. 30 to col 5, I. 38; U.S. Pat. No.5,256,823, especially in col 4, I. 23 to col 5, I. 15; U.S. Pat. No.5,135,543, especially in col 4, I. 24 to col 5, I. 16; EP-A-818 193,especially on p. 2, I. 40 to p. 3, I. 26; U.S. Pat. No. 5,486,629,especially in col 2, I. 34 to col 5, I. 29; and EP-A-758 547, especiallyon p. 7, I. 48 to p. 8, I. 19.

The dyes of formula (1) may also be combined with acid dyes, for examplethe dyes which are known from the international names (Color index), ortrade names.

Preferred acid dyes which are useful for the combination with a dye offormula (1) are described in U.S. Pat. No. 6,248,314. They include RedColor No. 120, Yellow Color No. 4, Yellow Color No. 5, Red Color No.201, Red Color No. 227, Orange Color No. 205, Brown Color No. 201, RedColor No. 502, Red Color No. 503, Red Color No. 504, Red Color No. 506,Orange Color No. 402, Yellow Color No. 402, Yellow Color No. 406, YellowColor No. 407, Red Color No. 213, Red Color No. 214, Red Color No. 3,Red Color No. 104, Red Color No. 105(1), Red Color No. 106, Green ColorNo. 2, Green Color No. 3, Orange Color No. 207, Yellow Color No. 202(1),Yellow Color No. 202(2), Blue Color No. 202, Blue Color No. 203, BlueColor No. 205, Blue Color No. 2, Yellow Color No. 203, Blue Color No.201, Green Color No. 201, Blue Color NO. 1, Red Color No. 230(1), RedColor No. 231, Red Color No. 232, Green Color No. 204, Green Color No.205, Red Color No. 401, Yellow Color No. 403(1), Green Color No. 401,Green Color No. 402, Black Color No. 401 and Purple Color No. 401,especially Black Color No. 401, Purple Color 401, Orange Color No. 205.

These acid dyes may be used either as single component or in anycombination thereof.

Hair dye compositions comprising an acid dye are known. They are forexample described in “Dermatology”, edited by Ch. Culnan, H. Maibach,Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, TheScience of Hair Care, chapter 7, p. 248-250, especially on p. 253 and254.

Hair dye compositions which comprise an acid dye have a pH of 2-6,preferably 2-5, more preferably 2.5-4.0.

The dyes of formula (1) according to the present invention may alsoreadily be used in combination with acid dyes and/or adjuvants, forexample

-   -   acid dyes and an alkylene carbonate, as described in U.S. Pat.        No. 6,248,314, especially in examples 1 and 2;    -   acid hair dye compositions comprising various kinds of organic        solvents represented by benzyl alcohol as a penetrant solvent        have good penetrability into hair, as described in Japanese        Patent Application Laid-Open Nos. 210023/1986 and 101841/1995;    -   acid hair dye compositions with a water-soluble polymer or the        like to prevent the drooping of the hair dye composition, as        described for example in Japanese Patent Application Laid-Open        Nos. 87450/1998, 255540/1997 and 245348/1996;    -   acid hair dye compositions with a water-soluble polymer of        aromatic alcohols, lower alkylene carbonates, or the like as        described in Japanese Patent Application Laid-Open No.        53970/1998 and Japanese Patent Invention No. 23911/1973.

The dyes of formula (1) may also be combined with uncharged dyes, forexample selected from the group of the nitroanilines,nitrophenylenediamines, nitroaminophenols, anthra-quinones, indophenols,phenazines, phenothiazines, bispyrazolons, bispyrazol aza derivativesand methines.

Furthermore, the dyes of formula (1) may also be used in combinationwith oxidation dye systems.

Oxidation dyes, which, in the initial state, are not dyes but dyeprecursors are classified according to their chemical properties intodeveloper and coupler compounds.

Suitable oxidation dyes are described for example in

-   -   DE 19 959 479, especially in col 2, I. 6 to col 3, I. 11;    -   “Dermatology”, edited by Ch. Culnan, H. Maibach, Verlag Marcel        Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The        Science of Hair Care, chapter 8, on p. 264-267 (oxidation dyes);

Preferred developer compounds are for example primary aromatic amines,which are substituted in the para- or ortho-position with a substitutedor unsubstituted hydroxy- or amino residue, or diaminopyridinederivatives, heterocyclic hydrazones, 4-aminopyrazol derivatives,2,4,5,6-tetraminopyrimidine derivatives, or unsaturated aldehydes asdescribed in DE 19 717 224, especially on p. 2, I. 50 to I. 66 and on p.3 I. 8 to I. 12, or cationic developer compounds as described in WO00/43367, especially on p., 2 I. 27 to p. 8, I. 24, in particular on p.9, I. 22 to p. 11, I. 6.

Furthermore, developer compounds in their physiological compatible acidaddition salt form, such as hydrochloride or sulfate can be used.Developer compounds, which have aromatic OH radicals are also suitablein their salt form together with a base, such as alkalimetal-phenolates.

Preferred developer compounds are disclosed in DE 19959479, p. 2, I.8-29.

More preferred developer compounds are p-phenylendiamine,p-toluoylendiamine, p-, m- o-aminophenol,N,N-bis-(2-hydroxyethyl)-p-phenylenediamine sulfate,2-amino-4-hydroxy-ethylaminoanisole sulfate,hydroxyethyl-3,4-methylenedioxyaniline,1-(2′-hydroxyethyl)-2,5-diaminobenzene,2,6-dimethoxy-3,5-diamino-pyridine,hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine) hydrochloride,hydroxyethyl-p-phenylenediamine sulfate, 4-amino-3-methylphenol,4-methylaminophenol sulfate, 2-aminomethyl-4-aminophenol,4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazol, 4-amino-m-cresol,6-amino-m-cresol, 5-amino-6-chloro-cresol, 2,4,5,6-tetraminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine or 4-hydroxy-2,5,6-triaminopyrimidinesulfate.

Preferred coupler compounds are m-phenylendiamine derivatives,naphthole, resorcine and resorcine derivatives, pyrazolone andm-aminophenol derivatives, and most preferably the coupler compoundsdisclosed in DE 19959479, p. 1, I. 33 to p. 3, I. 11.

The dyes of formula (1) may also be used together with unsaturatedaldehydes as disclosed in DE 19 717 224 (p. 2, I. 50 to I. 66 and on p.3 I. 8 to I. 12) which may be used as direct dyes or, alternativelytogether with oxidation dye precursors.

Further preferred for a combination with a dye of formula (1) are thefollowing oxidation dye precursors:

-   -   the developer/-coupler combination 2,4,5,6-tetraminopyrimidine        and 2-methylresorcine for assessing of red shades;    -   p-toluenediamine and 4-amino-2-hydroxytoluene for assessing of        blue-violet shades;    -   p-toluenediamine and 2-amino-4-hydroxyethylaminoanisole for        assessing of blue shades;    -   p-toluenediamine and 2,4-diamino-phenoxyethynol for assessing of        blue shades;    -   methyl-4-aminophenol and 4-amino-2-hydroxytoluene for assessing        of orange shades;    -   p-toluenediamine and resorcine for assessing of brown-green        shades;    -   p-toluenediamine and 1-naphthol for assessing of blue-violet        shades, or    -   p-toluenediamine and 2-methylresorcine for assessing of        brown-gold shades.

Furthermore, autooxidizable compounds may be used in combination withthe dyes of formula (1).

Autooxidizable compounds are aromatic compounds with more than twosubstituents in the aomatic ring, which have a very low redox potentialand will therefore be oxidized when ex-posed to the air. The dyeingsobtained with these compounds are very stable and resistant to shampoo.

Autooxidizable compounds are for example benzene, indol, or indoline,especially 5,6-di-hydroxyindol or 5,6-dihydroxyindoline derivatives asdescribed in WO 99/20234, especially on p. 26, I. 10 to p. 28, I. 15, orin WO 00/28957 on p. 2, third paragraph.

Preferred autooxidizable benzene derivatives are1,2,4-trihydroxybenzene, 1-methyl-2,4,5-trihydroxybenzene,2,4-diamnio-6-methylphenol, 2-amino-4-methylaminophenol,2,5-diamino-4-methyl-phenol, 2,6-diamino-4-diethylaminophenol,2,6-diamino-1,4-dihydroxy-benzene, and the salts of these compounds,which are accessible with acid.

Preferred autooxidizable indol derivatives are 5,6-dihydroxyindol,2-methyl-5,6-dihydroxy-indol, 3-methyl-5,6-dihydroxyindole,1-methyl-5,6-dihydroxyindol, 2,3-dimethyl-5,6-dihydroxy-indol,5-methoxy-6-dihydroxyindol, 5-acetoxy-6-hydroixyindol,5,6-diacetoxyindol, acid of 5,6-dihydroxyindol-2-carbon acid, and thesalts of these compounds, which are accessible with acid.

The dyes of formula (1) may also be used in combination with naturallyoccurring dyes, such as henna red, henna neutral, henna black, chamomileblossom, sandalwood, black tea, Rhamnus frangula bark, sage, campechewood, madder root, catechu, sedre and alkanet root. Such dyeings aredescribed, for example, in EP-A-404 868, especially on p. 3, I. 55 to p.4, I. 9.

Furthermore, the dyes of formula (1) may also be used in combinationwith capped diazotised compounds.

Suitable diazotised compounds are for example the compounds of formulae(1)-(4) in WO 2004/019897 (bridging pages 1 and 2) and the correspondingwatersoluble coupling components (I)-(IV) as disclosed in the samereference.

Further preferred dyes or dye combinations which are useful for thecombination with a dye of formula (1) according to the present inventionare described in

(DC-01): WO 95/01772, wherein mixtures of at least two cationic dyes aredisclosed, especially p. 2, I. 7 to p. 4, I. 1, preferably p. 4, I. 35to p. 8, I. 21; formulations p. 11, last §-p. 28, I. 19;

(DC-02): U.S. Pat. No. 6,843,256, wherein cationic dyes are disclosed,especially the compounds of formulae (1), (2), (3) and (4) (col. 1, I.27-col. 3, I. 20, and preferably the compounds as prepared in theexamples 1 to 4 (col. 10, I. 42 to col. 13, I. 37; formulations col. 13,I. 38 to col. 15, I. 8;

(DC-03): EP 970 685, wherein direct dyes are described, especially p. 2,I. 44 to p. 9, I. 56 and preferably p. 9, I. 58 to p. 48, I. 12;processes for dyeing of keratin-containing fibers especially p. 50, I.15 to 43; formulations p. 50, I. 46 to p. 51, I. 40;

(DC-04): DE-A-19 713 698, wherein direct dyes are described, especiallyp. 2, I. 61 to p. 3, I. 43; formulations p. 5, I. 26 to 60;

(DC-05): U.S. Pat. No. 6,368,360, wherein directed dyes (col. 4, I. 1 tocol. 6, I. 31) and oxidizing agents (col. 6, I. 37-39) are disclosed;formulations col. 7, I. 47 to col. 9, I. 4;

(DC-06): EP 1 166 752, wherein cationic dyes (p. 3, I. 22-p. 4, I. 15)and anionic UV-absorbers (p. 4, I. 27-30) are disclosed; formulations p.7, I. 50-p. 9, I. 56;

(DC-07): EP 998,908, wherein oxidation dyeings comprising a cationicdirect dye and pyrazolo-[1,5-a]-pyrimidines (p. 2, I. 48-p. 4, I. 1) aredisclosed; dyeing formulations p. 47, I. 25 to p. 50, I. 29;

(DC-08): FR-2788432, wherein combinations of cationic dyes with Arianorsare disclosed, especially p. 53, I. 1 to p. 63, I. 23, more especiallyp. 51 to 52, most especially Basic Brown 17, Basic brown 16, Basic Red76 and Basic Red 118, and/or at least one Basic Yellow 57, and/or atleast one Basic Blue 99; or combinations of arianoren and/or oxidativedyes, especially p. 2, I. 16 to p. 3, I. 16; dyeing formulations on p.53, I. 1 to p. 63, I. 23;

(DC-09): DE-A-19 713 698, wherein the combinations of direct dyes andpermanent-wave fixing comprising an oxidation agent, an oxidation dyeand a direct dye are disclosed; especially p. 4, I. 65 to p. 5, I. 59;

(DC-10): EP 850 638, wherein developer compounds and oxidizing agentsare disclosed; especially p. 2, I. 27 to p. 7, I. 46 and preferably p.7, I. 20 to p. 9, I. 26; dyeing formulations p. 2, I. 3-12 and I. 30 top. 14, and p. 28, I. 35-p. 30, I. 20; preferably p. 30, I. 25-p. 32, I.30;

(DC-11): U.S. Pat. No. 6,190,421 wherein extemporaneous mixtures of acomposition (A) containing one or more oxidation dye precursors andoptionally one or more couplers, of a composition (B), in powder form,containing one or more direct dyes (col. 5, I. 40-col. 7, I. 14),optionally dispersed in an organic pulverulent excipient and/or amineral pulverulent excipient, and a composition (C) containing one ormore oxidizing agents are disclosed; formulations col. 8, I. 60-col. 9,I. 56;

(DC-12): U.S. Pat. No. 6,228,129, wherein a ready-to-use compositioncomprising at least one oxidation base, at least one cationic direct dyeand at least one enzyme of the 2-electron oxidoreductase type in thepresence of at least one donor for the said enzyme are disclosed;especially col. 8, I. 17-col. 13, I. 65; dyeing formulations in col. 2,I. 16 to col. 25, I. 55, a multi-compartment dyeing device is describedin col. 26, I, 13-24;

(DC-13): WO 99/20235, wherein compositions of at least one cationic dyeand at least one nitrated benzene dye with cationic direct dyes andnitro benzene direct dyes are described; on p. 2, I. 1 to p. 7, I. 9,and p. 39, I. 1 to p. 40 I. 11, preferably p. 8, I. 12 to p. 25 I. 6, p.26, I. 7 to p. 30, I. 15; p. 1, I. 25 to p. 8, I. 5, p. 30, I. 17 to p.34 I. 25, p. 8, I. 12 to p. 25 I. 6, p. 35, I. 21 to 27, especially onp. 36, I. 1 to p. 37;

(DC-14): WO 99/20234, wherein compositions comprising at least onedirect cationic dye and at least one autooxidisable dye, especiallybenzene, indol and indoline derivatives are described, preferably directdyes on p. 2, I. 19 to p. 26, I. 4, and autooxidisable dyes as disclosedespecially on p. 26, I. 10 to p. 28, I. 15; dyeing formulationsespecially on p. 34, I. 5 to p. 35, Ii 18;

(DC-15): EP 850 636, wherein oxidation dyeing compositions comprising atleast one direct dye and at least one meta-aminophenol derivative ascoupler component and at least one developer compound and an oxidizingagent are disclosed, especially p. 5, I. 41 to p. 7, I. 52, dyeingformulations p. 19, I. 50-p. 22, I. 12;

(DC-16): EP-A-850 637, wherein oxidation dyeing compositions comprisingat least one oxidation base selected from para-phenylenediamines andbis(phenyl)alkylenediamines, and the acid-addition salts thereof, atleast one coupler selected from meta-diphenols, and the acid-additionsalts thereof, at least one cationic direct dye, and at least oneoxidizing agent are disclosed, especially p. 6, I. 50 to p. 8, I. 44 aredisclosed; dyeing formulations p. 21, I. 30-p. 22, I. 57;

(DC-17): WO 99/48856, wherein oxidation dyeing compositions comprisingcationic couplers are disclosed, especially p. 9, I. 16-p. 13, I. 8, andp. 11, I. 20-p. 12, I. 13; dyeing formulations p. 36, I, 7-p. 39, I. 24;

(DC-18): DE 197 172 24, wherein dyeing agents comprising unsaturatedaldehydes and coupler compounds and primary and secondary amino groupcompounds, nitrogen-containing heterocyclic compounds, amino acids,oligopeptids, aromatic hydroxy compounds, and/or at least one CH-activecompound are disclosed p. 3, I. 42-p. 5 I. 25; dyeing formulations p. 8,I, 25-p. 9, I. 61.

In the dye combinations disclosed in the references (DC-01-DC-18) above,the dyes of formula (1) according to the present invention may be addedto the dye combinations or dyeing formulations or may be replaced withat least one dye of formula (1).

The present invention also relates to formulations, which are used forthe dyeing of organic materials, preferably keratin-containing fibers,and most preferably human hair, comprising at least one dye of formula(1).

Preferably the dyes of formula (1) are incorporated into the compositionfor treating organic material, preferably for dyeing in amounts of0.001-5% b.w. (hereinafter indicated merely by “%”), particularly0.005-4%, more particularly 0.2-3%, based on the total weight of thecomposition.

The formulations may be applied on the keratin-containing fiber,preferably the human hair in different technical forms.

Technical forms of formulations are for example a solution, especially athickened aqueous or aqueous alcoholic solution, a cream, foam, shampoo,powder, gel, or emulsion. Customary the dyeing compositions are appliedto the keratin-containing fiber in an amount of 50 to 100 g.

Preferred forms of formulations are ready-to-use compositions ormulti-compartment dyeing devices or ‘kits’ or any of themulti-compartment packaging systems with compartments as described forexample in U.S. Pat. No. 6,190,421, col 2, I. 16 to 31.

The pH value of the ready-to-use dyeing compositions is usually from 2to 11, preferably from 5 to 10.

Preferably the dyeing compositions, which are not stable to reduction,are prepared with oxidizing agent free compositions just before thedyeing process.

One preferred embodiment of the present invention relates to theformulation of dyes, wherein the dyes of formula (1) are in powder form.

Powder formulations are preferably used if stability and/or solubilityproblems as for example described in DE 197 13 698, p. 2, I. 26 to 54and p. 3, I. 51 to p. 4, I. 25, and p. 4, I. 41 to p. 5 I. 59.

Suitable cosmetic hair-care formulations are hair-treatmentpreparations, e.g. hair-washing preparations in the form of shampoos andconditioners, hair-care preparations, e.g. pre-treatment preparations orleave-on products such as sprays, creams, gels, lotions, mousses andoils, hair tonics, styling creams, styling gels, pomades, hair rinses,treatment packs, intensive hair treatments, hair-structuringpreparations, e.g. hair-waving preparations for per-manent waves (hotwave, mild wave, cold wave), hair-straightening preparations, liquidhair-setting preparations, hair foams, hairsprays, bleachingpreparations, e.g. hydrogen peroxide solutions, lightening shampoos,bleaching creams, bleaching powders, bleaching pastes or oils,temporary, semi-permanent or permanent hair colorants, preparationscontaining self-oxidizing dyes, or natural hair colorants, such as hennaor chamomile.

For use on human hair, the dyeing compositions of the present inventioncan usually be incorporated into an aqueous cosmetic carrier. Suitableaqueous cosmetic carriers include, for example W/O, O/W, O/W/O, W/O/W orPIT emulsions and all kinds of microemulsions, creams, sprays,emulsions, gels, powders and also surfactant-containing foamingsolutions, e.g. shampoos or other preparations, that are suitable foruse on keratin-containing fibers. Such forms of use are described indetail in Research Disclosure 42448 (August 1999). If necessary, it isalso possible to incorporate the dyeing compositions into anhydrouscarriers, as described, for example, in U.S. Pat. No. 3,369,970,especially col 1, I. 70 to col 3, I. 55. The dyeing compositionsaccording to the invention are also excellently suitable for the dyeingmethod described in DE-A-3 829 870 using a dyeing comb or a dyeingbrush.

The constituents of the aqueous carrier are present in the dyeingcompositions of the present invention in the customary amounts, forexample emulsifiers may be present in the dyeing compositions inconcentrations from 0.5 to 30% b.w. and thickeners in concentrationsfrom 0.1 to 25% b.w. of the total dyeing composition.

Further carriers for dyeing compositions are for example described in“Dermatology”, edited by Ch. Culnan, H. Maibach, Verlag Marcel DekkerInc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of HairCare, chapter 7, p. 248-250, especially on p. 243, I. 1 to p. 244, I.12.

A shampoo has, for example, the following composition:

0.01 to 5% b.w. of a dye of formula (1);

8% b.w of disodium PEG-5 laurylcitrate Sulfosuccinate, Sodium LaurethSulfate;

20% b.w. of sodium cocoamphoacetate;

0.5% b.w. of methoxy PEG/PPG-7/3 aminopropyl dimethicone;

0.3% b.w. of hydroxypropyl guar hydroxypropytrimonium chloride;

2.5% b.w. of PEG-200 hydrogenated glyceryl palmate; PEG-7 glycerylcocoate;

0.5% b.w. of PEG-150 distearate;

2.2. % b.w of citric acid;

perfume, preservatives; and

water ad 100%.

The dyes of formula (1) may be stored in a liquid to paste-likepreparation (aqueous or non-aqueous) or in the form of a dry powder.

When the dyes and adjuvants are stored together in a liquid preparation,the preparation should be substantially anhydrous in order to reducereaction of the compounds.

The dyeing compositions according to the invention may comprise anyactive ingredients, additives or adjuvants known for such preparations,like surfactants, solvents, bases, acids, perfumes, polymeric adjuvants,thickeners and light stabilisers.

The following adjuavents are preferably used in the hair dyeingcompositions of the present invention:

-   -   non-ionic polymers, for example vinylpyrrolidone/vinyl acrylate        copolymers, polyvinyl-pyrrolidone and vinylpyrrolidone/vinyl        acetate copolymers and polysiloxanes;    -   cationic polymers, such as quaternised cellulose ethers,        polysiloxanes having quaternary groups, dimethyldiallylammonium        chloride polymers, copolymers of dimethyldiallyl-ammonium        chloride and acrylic acid, as available commercially under the        name Merquat® 280 and the use thereof in hair dyeing as        described, for example, in DE-A-4 421 031, especially p. 2, I.        20 to 49, or EP-A-953 334;    -   acrylamide/dimethyldiallylammonium chloride copolymers,        diethyl-sulfate-quaternised dimethylaminoethyl        methacrylate/vinylpyrrolidone copolymers,        vinylpyrrolidone/-imidazolinium methochloride copolymers;    -   quaternised polyvinyl alcohol:    -   zwitterionic and amphoteric polymers, such as        acrylamido-propyltrimethylammonium chloride/acrylate copolymers        and octylacrylamide/methyl methacrylate/tert-butylaminoethyl        methacrylate/2-hydroxypropyl methacrylate copolymers;    -   anionic polymers, such as, for example, polyacrylic acids,        crosslinked polyacrylic acids, vinyl acetate/crotonic acid        copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl        acetate/butyl maleate/isobornyl acrylate copolymers, methyl        vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl        acrylate/N-tert-butyl acrylamide terpolymers;    -   thickeners, such as agar, guar gum, alginates, xanthan gum, gum        arabic, karaya gum, locust bean flour, linseed gums, dextrans,        cellulose derivatives, e.g. methyl cellulose, hydroxyalkyl        cellulose and carboxymethyl cellulose, starch fractions and        derivatives, such amylose, amylopectin and dextrins, clays, e.g.        bentonite or fully synthetic hydro-colloids such as, for        example, polyvinyl alcohol;    -   structuring agents, such as glucose and maleic acid;    -   hair-conditioning compounds, such as phospholipids, for example        soya lecithin, egg lecithin, cephalins, silicone oils, and        conditioning compounds, such as those described in DE-A-19 729        080, especially p. 2, I. 20 to 49, EP-A-834 303, especially p.        2, I, 18-p. 3, I. 2, or EP-A-312 343, especially p. 2, I. 59-p.        3, I. 11;    -   protein hydrolysates, especially elastin, collagen, keratin,        milk protein, soya protein and wheat protein hydrolysates,        condensation products thereof with fatty acids and also        quaternised protein hydrolysates;    -   perfume oils, dimethyl isosorbitol and cyclodextrins,    -   solubilisers, such as ethanol, isopropanol, ethylene glycol,        propylene glycol, glycerol and diethylene glycol,    -   anti-dandruff active ingredients, such as piroctones, olamines        and zinc Omadine,    -   substances for adjusting the pH value;    -   panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic        acids and salts thereof, plant extracts and vitamins;    -   cholesterol;    -   light stabilisers and UV absorbers as listed in Table below:

TABLE 2 UV absorbers which may be use in the dyeing compositions of thepresent invention No. Chemical Name CAS No. 1(+/−)-1,7,7-trimethyl-3-[(4-methylphenyl)methylene]bicyclo- 36861-47-9[2.2.1]heptan-2-one 21,7,7-trimethyl-3-(phenylmethylene)bicyclo[2.2.1]heptan-2-one 15087-24-83 (2-Hydroxy-4-methoxyphenyl)(4-methylphenyl)methanone 1641-17-4 42,4-dihydroxybenzophenone 131-56-6 5 2,2′,4,4′-tetrahydroxybenzophenone131-55-5 6 2-Hydroxy-4-methoxy benzophenone; 131-57-7 72,2′-dihydroxy-4,4′-dimethoxybenzophenone 131-54-4 82,2′-Dihydroxy-4-methoxybenzophenone 131-53-3 91-[4-(1,1-dimethylethyl)phenyl]-3-(4-methoxyphenyl)propane-1,3-70356-09-1 dione 10 3,3,5-Trimethyl cyclohexyl-2-hydroxy benzoate118-56-9 11 Isopentyl p-methoxycinnamate 71617-10-2 12Menthyl-o-aminobenzoate 134-09-8 13 Menthyl salicylate 89-46-3 142-Ethylhexyl 2-cyano,3,3-diphenylacrylate 6197-30-4 15 2-ethylhexyl4-(dimethylamino)benzoate 21245-02-3 16 2-ethylhexyl 4-methoxycinnamate5466-77-3 17 2-ethylhexyl salicylate 118-60-5 18 Benzoic acid,4,4′,4″-(1,3,5-triazine-2,4,6-triyltriimino)tris-tris(2- 88122-99-0ethylhexyl)ester; 2,4,6-Trianilino-(p-carbo-2′-ethylhexyl-1′-oxi)-1,3,5-triazine 19 Benzoic acid, 4-amino-, ethyl ester, polymer withoxirane 113010-52-9 20 2-Propenamide,N-[[4-[(4,7,7-trimethyl-3-oxobicyclo[2.2.1]hept-2- 147897-12-9ylidene)methyl]phenyl]methyl]-, homopolymer 21 Triethanolaminesalicylate 2174-16-5 222,2′-Methylene-bis-[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethyl-103597-45-1 butyl)-phenol] 232,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxy-187393-00-6 phenyl)-(1,3,5)-triazine (Tinosorb S) 24 Benzoic acid,4,4′-[[6-[[4-[[(1,1-dimethylethyl)amino]carbonyl]- 154702-15-5phenyl]amino]1,3,5-triazine-2,4-diyl]diimino]bis-, bis(2-ethylhexyl)-ester 25 Phenol,2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3- 155633-54-8tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]- 26Dimethicodiethylbezalmalonate 207574-74-1 27 Benzoic acid,2-[4-(diethylamino)-2-hydroxybenzoyl]-, hexyl ester 302776-68-7 281,3,5-Triazine, 2,4,6-tris(4-methoxyphenyl)- 7753-12-0 291,3,5-Triazine, 2,4,6-tris[4-[(2-ethylhexyl)oxy]phenyl]- 208114-14-1 302-Propenoic acid, 3-(1H-imidazol-4-yl)- 104-98-3 31 Benzoic acid,2-hydroxy-, [4-(1-methylethyl)phenyl]methyl ester 94134-93-7 321,2,3-Propanetriol, 1-(4-aminobenzoate) 136-44-7 33 Benzeneacetic acid,3,4-dimethoxy-a-oxo- 4732-70-1 34 2-Propenoic acid,2-cyano-3,3-diphenyl-, ethyl ester 5232-99-5 35 Anthralinic acid,p-menth-3-yl ester 134-09-8 36 1,3,5-Triazine-2,4,6-triamine,N,N′-bis[4-[5-(1,1-dimethylpropyl)-2- 288254-16-0benzoxazolyl]phenyl]-N″-(2-ethylhexyl)- or Uvasorb K2A 372-Hydroxy-4-methoxy benzophenone-5-sulfonic acid 4065-45-6 38Alpha-(2-oxoborn-3-ylidene)toluene-4-sulphonic acid and its salts56039-58-8 39 MethylN,N,N-trimethyl-4-[(4,7,7-trimethyl-3-oxobicyclo[2,2,1]hept- 52793-97-22-ylidene)methyl]anilinium sulphate; 40 4-aminobenzoic acid 150-13-0 412-phenyl-1H-benzimidazole-5-sulphonic acid 27503-81-7 423,3′-(1,4-phenylenedimethylene)bis[7,7-dimethyl-2-oxo-bicyclo-90457-82-2 [2.2.1]heptane-1-methanesulfonic acid] 431H-Benzimidazole-4,6-disulfonic acid, 2,2′-(1,4-phenylene)bis-,180898-37-7 disodium salt 44 Benzenesulfonic acid,3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1- 92484-48-5 methylpropyl)-,monosodium salt 45 1-Dodecanaminium,N-[3-[[4-(dimethylamino)benzoyl]amino]pro- 156679-41-3pyl]N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1) 461-Propanaminium, N,N,N-trimethyl-3-[(1-oxo-3-phenyl-2-propenyl)-177190-98-6 amino]-, chloride 47 1H-Benzimidazole-4,6-disulfonic acid,2,2′-(1,4-phenylene)bis- 170864-82-1 48 1-Propanaminium,3-[[3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethyl- 340964-15-0ethyl)-4-hydroxyphenyl]-1-oxopropyl]amino]-N,N-diethyl-N-methyl-, methylsulfate (salt) 492,2′-bis(1,4-phenylene)-1H-benzimidazole-4,6-disulphonic acid mo-349580-12-7, no sodium salt or Disodium phenyl dibenzimidazoletetrasulfonate or Neoheliopan AP

The use of UV absorbers can effectively protect natural and dyed hairfrom the damaging rays of the sun and increase the wash fastness of dyedhair.

Furthermore, the following UV absorbers or combinations may be used inthe dyeing compositions according to the invention:

-   -   cationic benzotriazole UV absorbers as for example described in        WO 01/36396 especially on p. 1, I. 20 to p. 2, I. 24, and        preferred on p. 3 to 5, and on p. 26 to 37;    -   cationic benzotriazole UV in combination with antioxidants as        described in WO 01/36396, especially on p. 11, I. 14 to p. 18;    -   UV absorbers in combination with antioxidants as described in        U.S. Pat. No. 5,922,310, especially in col 2, I. 1 to 3;    -   UV absorbers in combination with antioxidants as described in        U.S. Pat. No. 4,786,493, especially in col 1, 42 to col 2, I. 7,        and preferred in col 3, 43 to col 5, I. 20;    -   combination of UV absorbers as described in U.S. Pat. No.        5,830,441, especially in col 4, I. 53 to 56;    -   combination of UV absorbers as described in WO 01/36396,        especially on p. 11, I. 9 to 13; or    -   triazine derivatives as described in WO 98/22447, especially        on p. 1, I. 23 to p. 2, I. 4, and preferred on p. 2, I. 11 to p.        3, I. 15 and most preferred on p. 6 to 7, and 12 to 16.

Suitable cosmetic preparations may usually contain 0.05 to 40% b.w.,preferably from 0.1 to 20% b.w., based on the total weight of thecomposition, of one or more UV absorbers;

-   -   consistency regulators, such as sugar esters, polyol esters or        polyol alkyl ethers;    -   fats and waxes, such as spermaceti, beeswax, montan wax,        paraffins, fatty alcohols and fatty acid esters;    -   fatty alkanolamides;    -   polyethylene glycols and polypropylene glycols having a        molecular weight from 150 to 50 000, for example such as those        described in EP-A-801 942, especially p. 3, I. 44 to 55,    -   complexing agents, such as EDTA, NTA and phosphonic acids,    -   swelling and penetration substances, such as polyols and polyol        ethers, as listed extensively, for example, in EP-A-962 219,        especially p. 27, I. 18 to 38, for example glycerol, propylene        glycol, propylene glycol monoethyl ether, butyl glycol, benzyl        alcohol, carbonates, hydrogen carbonates, guanidines, ureas and        also primary, secondary and tertiary phosphates, imidazoles,        tannins, pyrrole;    -   opacifiers, such as latex;    -   pearlising agents, such as ethylene glycol mono- and        di-stearate;    -   propellants, such as propane-butane mixtures, N₂O, dimethyl        ether, CO₂ and air;    -   antioxidants; preferably the phenolic antioxidants and hindered        nitroxyl compounds disclosed in ip.com (IPCOM # 000033153D);    -   sugar-containing polymers, as described in EP-A-970 687;    -   quaternary ammonium salts, as described in WO 00/10517;    -   Bacteria inhibiting agents, like preservatives that have a        specific action against gram-positive bacteria, such as        2,4,4′-trichloro-2′-hydroxydiphenyl ether, chlorhexidine        (1,6-di(4-chlorophenyl-biguanido)hexane) or TCC        (3,4,4′-trichlorocarbanilide). A large number of aromatic        substances and ethereal oils also have antimicrobial properties.        Typical examples are the active ingredients eugenol, menthol and        thymol in clove oil, mint oil and thyme oil. A natural        deodorizing agent of interest is the terpene alcohol farnesol        (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in        lime blossom oil. Glycerol monolaurate has also proved to be a        bacteriostatic agent. The amount of the additional        bacteria-inhibiting agents present is usually from 0.1 to 2%        b.w., based on the solids content of the preparations;

The dyeing compositions according to the present invention generallycomprise at least one surfactant.

Suitable surfactants are zwitterionic or ampholytic, or more preferablyanionic, non-ionic and/or cationic surfactants.

Suitable anionic surfactants in the dyeing compositions according to thepresent invention include all anionic surface-active substances that aresuitable for use on the human body. Such substances are characterised byan anionic group that imparts water solubility, for example acarboxylate, sulfate, sulfonate or phosphate group, and a lipophilicalkyl group having approximately 10 to 22 carbon atoms. In addition,glycol or polyglycol ether groups, ester, ether and amide groups andalso hydroxy groups may be present in the molecule. The following areexamples of suitable anionic surfactants, each in the form of sodium,potassium or ammonium salts or mono-, di- or tri-alkanolammonium saltshaving 2 or 3 carbon atoms in the alkanol group:

-   -   linear fatty acids having 10 to 22 carbon atoms (soaps),    -   ether carboxylic acids of formula R—O—(CH₂—CH₂—O)_(x)—CH₂—COOH,        in which R is a linear alkyl group having 10 to 22 carbon atoms        and x=0 or from 1 to 16,    -   acyl sarcosides having 10 to 18 carbon atoms in the acyl group,    -   acyl taurides having 10 to 18 carbon atoms in the acyl group,    -   acyl isothionates having 10 to 18 carbon atoms in the acyl        group,    -   sulfosuccinic mono- and di-alkyl esters having 8 to 18 carbon        atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethyl        esters having 8 to 18 carbon atoms in the alkyl group and from 1        to 6 oxyethyl groups,    -   linear alkane sulfonates having 12 to 18 carbon atoms,    -   linear α-olefin sulfonates having 12 to 18 carbon atoms,    -   α-sulfo fatty acid methyl esters of fatty acids having 12 to 18        carbon atoms,    -   alkyl sulfates and alkyl polyglycol ether sulfates of formula        R′—O(CH₂—CH₂—O)_(x)—SO₃H, in which R′ is a preferably linear        alkyl group having 10 to 18 carbon atoms and x′=0 or from 1 to        12,    -   mixtures of surface-active hydroxysulfonates according to DE-A-3        725 030;    -   sulfated hydroxyalkylpolyethylene and/or        hydroxyalkylenepropylene glycol ethers according to DE-A-3 723        354, especially p. 4, I. 42 to 62,    -   sulfonates of unsaturated fatty acids having 12 to 24 carbon        atoms and 1 to 6 double bonds according to DE-A-3 926 344,        especially p. 2, I. 36 to 54,    -   esters of tartaric acid and citric acid with alcohols which are        addition products of approximately from 2 to 15 molecules of        ethylene oxide and/or propylene oxide with fatty alcohols having        from 8 to 22 carbon atoms, or    -   anionic surfactants, as described in WO 00/10518, especially p.        45, I. 11 to p. 48, I. 3.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ethersulfates and ether carboxylic acids having 10 to 18 carbon atoms in thealkyl group and up to 12 glycol ether groups in the molecule, and alsoespecially salts of saturated and especially unsaturatedC₈-C₂₂carboxylic acids, such as oleic acid, stearic acid, isostearicacid and palmitic acid.

Surface-active compounds that carry at least one quaternary ammoniumgroup and at least one —COO⁻ or —SO₃ ⁻ group in the molecule areterminated zwitterionic surfactants. Preference is given the so-calledbetaines, such as the N-alkyl-N,N-dimethylammonium glycinates, forexample cocoalkyldimethylammonium glycinate,N-acylaminopropyl-N,N-dimethylammonium glycinates, for examplecocoacylaminopropyldimethylammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethylimidazoline having from 8 to 18carbon atoms in the alkyl or acyl group and alsococoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferredzwitterionic surfactant is the fatty acid amide derivative known by theCTFA name cocoamidopropyl betaine.

Ampholytic surfactants are surface-active compounds that, in addition toa C₈-C₁₈-alkyl or -acyl group and contain at least one free amino groupand at least one —COOH or —SO₃H group in the molecule and are capable offorming internal salts. Examples of suitable ampholytic surfactantsinclude N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyricacids, N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids, each having approximately from 8 to 18 carbon atoms in the alkylgroup. Ampholytic surfactants to which special preference is given areN-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate andC₁₂-C₁₈acylsarcosine.

Suitable non-ionic surfactants are described in WO 00/10519, especiallyp. 45, I. 11 to p. 50, I. 12. Non-ionic surfactants contain ashydrophilic group, for example, a polyol group, a poly-alkylene glycolether group or a combination of polyol and polyglycol ether groups. Suchcompounds are, for example:

-   -   addition products of 2 to 30 mol of ethylene oxide and/or 0 to 5        mol of propylene oxide with linear fatty alcohols having 8 to 22        carbon atoms, with fatty acids having 12 to 22 carbon atoms and        with alkylphenols having 8 to 15 carbon atoms in the alkyl        group,    -   C₁₂-C₂₂ fatty acid mono- and di-esters of addition products of 1        to 30 mol of ethylene oxide with glycerol,    -   C₈-C₂₂alkyl-mono- and -oligo-glycosides and ethoxylated        analogues thereof,    -   addition products of 5 to 60 mol of ethylene oxide with castor        oil and hydrogenated castor oil,    -   addition products of ethylene oxide with sorbitan fatty acid        esters,    -   addition products of ethylene oxide with fatty acid        alkanolamides.

The surfactants which are addition products of ethylene and/or propyleneoxide with fatty alcohols or derivatives of such addition products mayeither be products having a “normal” homologue distribution or productshaving a restricted homologue distribution. “Normal” homologuedistribution are mixtures of homologues obtained in the reaction offatty alcohol and alkylene oxide using alkali metals, alkali metalhydroxides or alkali metal alcoholates as catalysts. Restrictedhomologue distributions, on the other hand, are obtained when, forexample, hydrotalcites, alkali metal salts of ether carboxylic acids,alkali metal oxides, hydroxides or alcoholates are used as catalysts.

The use of products having restricted homologue distribution may bepreferred.

Examples of cationic surfactants that can be used in the dyeingcompositions according to the invention are especially quaternaryammonium compounds. Preference is given to ammonium halides, such asalkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides andtrialkylmethylammonium chlorides, for example cetyltrimethylammoniumchloride, stearyltrimethylammonium chloride, distearyldimethyl-lammoniumchloride, lauryldimethylammonium chloride, lauryldimethylbenzylammoniumchloride and tricetylmethylammonium chloride. Further cationicsurfactants that can be used in accordance with the invention arequaternised protein hydrolysates.

Also suitable are cationic silicone oils, such as, for example, thecommercially available products Q2-7224 (manufacturer: Dow Corning; astabilised trimethylsilylamodimethicone), Dow Corning 929 emulsion(comprising a hydroxylamino-modified silicone, which is also referred toas amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067(manufacturer: Wacker) and also Abil®-Quat 3270 and 3272 (manufacturer:Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80), orsilicones, as described in WO 00/12057, especially p. 45, I. 9 to p. 55,I. 2.

Alkylamidoamines, especially fatty acid amidoamines, such as thestearylamidopropyl-dimethylamine obtainable under the name Tego Amid® 18are also preferred as surfactants in the present dyeing compositions.They are distinguished not only by a good conditioning action but alsoespecially by their good biodegradability.

Quaternary ester compounds, so-called “esterquats”, such as the methylhydroxyalkyl-dialkoyloxyalkylammonium methosulfates marketed under thetrademark Stepantex®, are also very readily biodegradable.

An example of a quaternary sugar derivative that can be used as cationicsurfactant is the commercial product Glucquat 100, according to CTFAnomenclature a “lauryl methyl gluceth-10 hydroxypropyl dimoniumchloride”.

The alkyl-group-containing compounds used as surfactants may be singlesubstances, but the use of natural raw materials of vegetable or animalorigin is generally preferred in the preparation of such substances,with the result that the substance mixtures obtained have differentalkyl chain lengths according to the particular starting material used.

The dyes of formula (1) are suitable for the dyeing of organic material,perferably keratin-containing fibers.

A further preferred embodiment of the present invention relates to amethod of treating keratin-containing fibers with a thiol dye of formula(1).

The process comprises

(a) contacting the keratin fiber with at least a compound of formula(1),

(b) leaving the fibers to stand, and

(c) then rinsing the fiber.

The process for dyeing is for example described in WO 01/66646 on page15, line 32 to page 16, line 2.

A further preferred method comprises treating the hair in the presenceof a reduction agent.

Preferred reduction agents are for example thioglycol acid or saltsthereof, gycerine monothioglycolat, cystein, 2-mercaptopropionic acid,2-mercaptoethylamine, thiolactic acid, thioglycerine, sodium sulfite,dithionithe, ammonium sulfite, sodium bisulfite, sodium metabisulfite,hydroquinone, phosphines, borhydride, cyanoborohydride, triacetoxyborohydride, trimethoxy borohydride salts (sodium, lithium, potassium,calcium auaternary salts).

Furthermore, the present invention relates to a process, comprisingtreating the hair with

(a) optionally a reduction agent,

(b) The dyes of the present invention s defined above, and

(c) with an oxidizing agent.

The step (a) may be of short duration from 0.1 sec to 30 minutes, froexample from 0.1 seconds to 10 minutes with a reducing agent mentionedabove.

The application of the dyes on the hair may be carried out attemperatures ranging from 15° to 100° C. Generally the application iscarried out at room temperature.

The sequence of the reaction steps is generally not important; thereduction agent can be applied first or in a final step.

Usually, the oxidizing agent is applied together with an acid or a base.

The acid is for example citric acid, phosphoric acid or tartrate acid.

The base is for example sodium hydroxide, ammonia or monoethanolamine.

The dyes of formula (1) are suitable for all-over dyeing of the hair,that is to say when dyeing the hair on a first occasion, and also forre-dyeing subsequently, or dyeing of locks or parts of the hair.

The dyes of formula (1) are applied on the hair for example by massagewith the hand, a comb, a brush, or a bottle, or a bottle, which iscombined with a comb or a nozzle.

Further preferred is a process for dyeing keratin-containing fiberswhich comprises treating the keratin-containing fiber with at least onedye of formula (1), a base and an oxidizing agent.

The oxidation dyeing process usually involves lightening, that is to saythat it involves applying to the keratin-containing fibers, at basic pH,a mixture of bases and aqueous hydrogen peroxide solution, leaving theapplied mixture to stand on the hair and then rinsing the hair. Itallows, particularly in the case of hair dyeing, the melanin to belightened and the hair to be dyed.

Lightening the melanin has the advantageous effect of creating a unifieddyeing in the case of grey hair, and, in the case of naturally pigmentedhair, of bringing out the color, that is to say of making it morevisible.

In general, the oxidizing agent containing composition is left on thefiber for 0.1 to 15 minutes, in particular for 0.1 to 5 minutes at 15 to45° C., usually in amounts of 30 to 200 g.

Oxidizing agents are for example persulfate or diluted hydrogen peroxidesolutions, hydrogen peroxide emulsions or hydrogen peroxide gels,alkaline earth metal peroxides, organic peroxides, such as ureaperoxides, melamine peroxides. Alkalimetalbromate fixations or enzymesare also appropriate if a shading powder on the basis of semi-permanent,direct hair dyes is used.

Further preferred oxidizing agents are

-   -   oxidizing agents to achieve lightened coloration, as described        in WO 97/20545, especially p. 9, I. 5 to 9,    -   oxidizing agents in the form of permanent-wave fixing solution,        as described in DE-A-19 713 698, especially p. 4, I. 52 to 55,        and I. 60 and 61 or EP-A-1062940, especially p. 6, I. 41 to 47        (and in the equivalent WO 99/40895).

Most preferred oxidizing agent is hydrogen peroxide, preferably used ina concentration from about 2 to 30%, more preferably about 3 to 20% by,and most preferably from 6 to 12% b.w. the corresponding composition.

The oxidizing agents may be present in the dyeing compositions accordingto the invention preferably in an amount from 0.01% to 6%, especiallyfrom 0.01% to 1%, based on the total dyeing composition.

In general, the dyeing with an oxidative agent is carried out in thepresence of a base, for example ammonia, alkali metal carbonates, earthmetal (potassium or lithium) carbonates, alkanol amines, such as mono-,di- or triethanolamine, alkali metal (sodium) hydroxides, earth metalhydroxides or compounds of the formula

wherein

R is a propylene residue, which may be substituted with OH orC₁-C₄alkyl,

R₃, R₄, R₅ and R₆ are independently or dependently from each otherhydrogen, C₁-C₄alkyl or hydroxy-(C₁-C₄)alkyl.

The pH-value of the oxidizing agent containing composition is usuallyabout 2 to 7, and in particular about 2 to 5.

One preferred method of applying formulations comprising the dyes offormula (1) on the keratin-containing fiber, preferably the hair is byusing a multi-compartment dyeing device or “kit” or any othermulti-compartment packaging system, as described for example in WO97/20545 on p. 4, I. 19 to I. 27.

The first compartment contains for example at least one dye of formula(1) and optionally further direct dyes and a basifying agent, and in thesecond compartment an oxidizing agent; or in the first compartment atleast one dye of formula (1) and optionally further direct dyes, in thesecond compartment a basifiying agent and in the third compartment anoxidizing agent.

A further preferred embodiment of the present invention relates to amethod of dyeing hair with oxidative dyes, which comprises

-   -   (a) mixing at least one dye of formula (1) and optionally at        least one coupler compound and at least one developer compound,        and an oxidizing agent, which optionally contains at least one        further dye, and    -   (b) contacting the keratin-containing fibers with the mixture as        prepared in step (a).

The pH-value of the oxidizing agent free composition is usually from 3to 11, and in particular from 5 to 10, and most particular about 9 to10.

Preferably, a ready-to-use composition is prepared according to a firstpreferred embodiment by a process which comprises a preliminary stepwhich involves separately storing, on the one hand, a composition (A)comprising, in a medium which is suitable for dyeing, at least onedeveloper compound, especially selected from para-phenylenediamines andbis(phenyl)-alkylenediamines, and the acid-addition salts thereof, atleast one coupler, especially selected from meta-phenylenediamines andthe acid-addition salts thereof, and at least one dye of formula (1), onthe other hand, a composition (B) containing, in a medium which issuitable for dyeing, at least one oxidizing agent and mixing (A) and (B)together immediately before applying this mixture to thekeratin-containing fibers.

According to a second preferred embodiment for the preparation of theready-to-use dye composition, the process includes a preliminary stepwhich involves separately storing, on the one hand, a composition (A)comprising, in a medium which is suitable for dyeing, at least onedeveloper compound, especially selected from para-phenylenediamines andbis-(phenyl)alkylenediamines, and the acid-addition salts thereof, atleast one coupler compound, especially selected frommeta-phenylenediamines and the acid-addition salts thereof; on the otherhand, a composition (A′) comprising, in a medium which is suitable fordyeing, at least one dye of formula (1), and, finally, a composition (B)containing, in a medium which is suitable for dyeing, at least oneoxidizing agent as defined above, and mixing them together at the timeof use immediately before applying this mixture to thekeratin-containing fibers.

The composition (A′) used according to this second embodiment mayoptionally be in powder form, the dye(s) of formula (1) (themselves)constituting, in this case, all of the composition (A′) or optionallybeing dispersed in an organic and/or inorganic pulverulent excipient.

When present in the composition A′, the organic excipient may be ofsynthetic or natural origin and is selected in particular fromcrosslinked and non-crosslinked synthetic polymers, polysaccharides suchas celluloses and modified or unmodified starches, as well as naturalproducts such as sawdust and plant gums (guar gum, carob gum, xanthangum, etc.).

When present in the composition (A′), the inorganic excipient maycontain metal oxides such as titanium oxides, aluminium oxides, kaolin,talc, silicates, mica and silicas.

A-very suitable excipient in the dyeing compositions according to theinvention is sawdust.

The powdered composition (A′) may also contain binders or coatingproducts in an amount which preferably does not exceed approximately 3%b.w. relative to the total weight of composition (A′). These binders arepreferably selected from oils and liquid fatty substances of inorganic,synthetic, animal or plant origin.

Furthermore, the present invention relates to a process of dyeing ofkeratin-containing fibers of the dyes of formula (1) with autooxidablecompounds and optionally further dyes.

Furthermore, the present invention relates to a process for dyeingkeratin-containing fibers with the dyes of formula (1) and cappeddiazotised compounds, which comprises,

-   (a) treating the keratin-containing fibers under alkaline conditions    with at least one capped diazotised compound and a coupler compound,    and optionally a developer compound ad optionally an oxidizing    agent, and optionally in the presence of a further dye, and    optionally with at least one dye of formula (1); and-   (b) adjusting the pH in the range of 6 to 2 by treatment with an    acid, optionally in the presence of a further dye, and optionally at    least one dye of formula (1),    with the proviso that at least in one step (a) or (b) at least one    dye of formula (1) is present.

The capped diazotised compound and coupler compound and optionally theoxidizing agent and developer compound can be applied in any desiredorder successively, or simultaneously.

Preferably, the capped diazotised compound and the coupler compound areapplied simultaneously, in a single composition.

“Alkaline conditions” denotes a pH in the range from 8 to 10, preferably9-10, especially 9.5-10, which are achieved by the addition of bases,for example sodium carbonate, ammonia or sodium hydroxide.

The bases may be added to the hair, to the dye precursors, the cappeddiazotised compound and/or the water-soluble coupling component, or tothe dyeing compositions comprising the dye precursors.

Acids are for example tartaric acid or citric acid, a citric acid gel, asuitable buffer solution with optionally an acid dye.

The ratio of the amount of alkaline dyeing composition applied in thefirst stage to that of acid dyeing composition applied in the secondstage is preferably about from 1:3 to 3:1, especially about 1:1.

Furthermore, the present invention relates to a process for dyeingkeratin-containing fibers with the dyes of formula (1) and at least oneacid dye.

The following Examples serve to illustrate the processes for dyeingwithout limiting the processes thereto. Unless specified otherwise,parts and percentages relate to weight. The amounts of dye specified arerelative to the material being coloured.

t, s, d, q and J, wherein t is a triplett, s is singulett, d is duplett,q is a quartett, and J is a coupling constant, define the NMR spectravalues.

EXAMPLES A. Preparation Examples Example 1 1a: Preparation of theCompound of Formula

(a) Condensation

35.7 g 1,3,3 trimethyl-2-methylene-indoline are added to 60 g aceticacid.

The equivalent amount (35.0 g) of 2-chloroethyl-methylamino-benzaldehydeis added and the reaction mixture stirred for 6 h at 30-40° C.

The reaction product is precipitated by cooling, diluted with 375 mlwater and salted out with 40 g sodium chloride, then separated byfiltration and dried in vacuum to obtain 65 g of a reddish violet solidproduct.

The product is recrystallized twice from methanol.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz:

9.65 s .03 benzal (trace) 8.328 d 6.7 1.00 vinyl 7.973 d 6.7 2.01 phe7.669 d 16.6 2.03 ind 7.58 m 6.1 1.04 ind 7.52 m 6.5 1.025 ind 7.04 d16.9 1.01 vinyl 6.976 d 6.4 2.00 phe 4.016 s 3.00 methyl 3.949 t 6 2.03ethylene 3.821 t 6 2.05 ethylene 3.257 s 3.087 methyl(amine) 1.8326 s6.04 di me-indis obtained.(b) Alkylation

One equivalent (10.0 g) sodium thiosulfate is dissolved in 30 g of thealkylating dye (101c) with 75 ml ethanol as solvent.

The temperature is raised to reflux and maintained at 80° C. during thefollowing 4 hours.

The product of formula

is obtained.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz

8.328 d 6.7 1.00 vinyl 7.973 d 6.7 2.01 phe 7.669 d 16.6 2.03 ind 7.58 m6.1 1.04 ind 7.52 m 6.5 1.025 ind 7.04 d 16.9 1.01 vinyl 6.976 d 6.42.00 phe 4.016 s 3.00 methyl 3.949 t 6 2.03 ethylene 3.821 t 6 2.05ethylene 3.257 s 3.087 methyl(amine) 1.8326 s 6.04 di me-ind(c) Hydrolysis

One equivalent (4,0 g) sodium hydroxide is dissolved with absoluteethanol as solvent in the compound (101b) as obtained in step (b).

The temperature is maintained at 80° C. during the following 4 hours.

The product is crystallized by cooling to room temperature under mixing,than separated by filtration, washed and dryed in vacuum dryer.

The compound of formula

is obtained.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz

8.82 d 6.7 1.00 vinyl 7.932 d 6.7 2.01 phe 7.645 d 16.6 2.03 ind 7.58 m6.1 1.04 ind 7.49 m 6.5 1.025 ind 7.215 d 16.9 1.01 vinyl 7.043 d 6.42.00 phe 3.978 s 3.00 methyl 3.949 t 6 2.03 ethylene 3.280 t 6 2.05ethylene 3.224 s 3.087 methyl(amine) 1.810 s 6.04 di me-ind

Example 2 Preparation of the Compound of Formula

(a) Alkylation

One equivalent (6.0 g) of thiourea is dissolved with absolute ethanol assolvent in 30 g of the alkylating dye of formula (101a).

The temperature is raised to reflux and maintained at 80° C. during thefollowing 48 hours. The product is crystallized by cooling to roomtemperature under mixing, than separated by filtration, washed and driedin vacuum dryer.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz

8.335 d 6.7 1.00 vinyl 7.997 d 6.7 2.01 Phe 7.669 d 16.6 2.03 Ind 7.58 m6.1 1.04 Ind 7.532 m 6.5 1.025 ind 7.32 d 16.9 1.01 vinyl 6.996 d 6.42.00 Phe 4.016 s 3.00 methyl 3.952 t 6 2.03 ethylene 3.548 t 6 2.05ethylene 3.235 s 3.087 methyl(amine) 1.826 s 6.04 Di Me-ind

Example 3 Preparation of the Compound of Formula

One equivalent (14.0 g) of ethyl xantogenate is dissolved with absoluteethanol as solvent in the alkylating dye of formula (101a).

The temperature is raised to reflux and maintained at 80° C. during thefollowing 8 hours.

The product is crystallized by cooling to room temperature under mixing,than separated by filtration, washed and dryed in vacuum dryer.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz

8.328 d 6.7 1.00 vinyl 7.990 d 6.7 2.03 phe 7.690 d 16.6 2.00 ind 7.58 m6.1 1.04 ind 7.54 m 6.5 1.025 ind 7.420 d 16.9 1.03 vinyl 7.00 d 6.42.00 phe 4.016 s 3.00 methyl 3.950 t 6 2.03 ethylene 3.504 t 6 2.05ethylene 3.257 s 3.087 methyl(amine) 1.822 s 6.04 di me-ind

Example 4 Preparation of the Compound of Formula

(a) Alkylation

68.8 g 4-methyl-pyridine are dissolved in 80 ml absolute ethanol assolvent.

The temperature is raised to 333 K.

94 g dimethylsulfate are introduced into that mixture within one hour.

The temperature is maintained at 333 K during the following 1.5 hours.

(b) Condensation

The equivalent amount (150.0 g) 2-chloroethyl-methylamino-benzaldehyde,250 ml ethanol and a catalytical amount (9.6 g) of piperidine are addedto the reaction mixture obtained in step (a) and the reaction mixturestirred for 8 hours at,

The reaction product is precipitated by cooling, then separated byfiltration and dried in vacuum to obtain 240 g of an orange solidproduct.

The product is recrystallized twice from methanol.

The product of formula

is obtained.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz

8.522 d 6.7 1.98 py 7.983 d 6.7 2.02 py 7.828 d 16.6 1.03 vinyl 7.632 d6.1 2.04 phe 7.112 d 16.9 1.00 vinyl 6.835 d 7.5 2.025 phe 4.234 s 3.03methyl 3.818 t 6 2.00 ethylene 3.748 t 6 2.05 ethylene 3.696 s 2.59 mms3.131 s 2.98 me am N(c):

One equivalent (6.0 g) thiourea is dissolved with 75 ml absolute ethanolas solvent in 20 g alkylating dye of formula (104a).

The temperature is raised to reflux and maintained at 80° C. during thefollowing 48 hours. The product is crystallized by cooling to roomtemperature under mixing, than separated by filtration, washed and driedin the vacuum dryer.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz

8.522 d 6.7 2.00 py 8.012 d 6.7 2.02 py 7.848 d 16.6 1.03 vinyl 7.662 d6.1 2.04 phe 7.152 d 16.9 1.00 vinyl 6.875 d 7.5 2.025 phe 4.248 s 3.03methyl 3.831 t 6 2.00 ethylene 3.696 s mms 3.480 t 6 2.09 ethylene 3.115s 2.98 me am N

Example 5 Preparatin of the Compound of Formula

One equivalent (8.0 g) of potassium thioacetate is dissolved withabsolute ethanol as solvent to 20 g of the alkylating dye of formula(104a).

The temperature is raised to reflux and maintained at 80° C. during thefollowing 4 hours.

The product is crystallized by cooling to room temperature under mixing,than separated by filtration, washed and dried in the vacuum dryer.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz

8.516 d 6.7 2.00 py 7.968 d 6.7 2.03 py 7.811 d 16.6 0.99 vinyl 7.620 d6.1 2.01 phe 7.085 d 16.9 1.00 vinyl 6.889 d 7.5 2.03 phe 4.223 s 3.03methyl 3.696 s 2.59 mms 3.581 t 6 1.80 ethylene 3.104 s 2.98 me am n3.084 t 6 1.90 ethylene 2.358 s 2.78 acetat

Example 6 Preparation of the Compound of Formula

One equivalent (6.0 g) thiourea was dissolved in absolute ethanol thecompound of formula (104a).

The temperature is raised to reflux and maintained at 80° C. during thefollowing 48 hours.

The obtained product is dissolved in one equivalent (4,0 g) of sodiumhydroxide with absolute ethanol.

The temperature is maintained at 80° C. during the following 4 hours.

The product is crystallized by cooling to room temperature under mixing,than separated by filtration, washed and dried in the vacuum dryer.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz

8.518 d 6.7 1.95 py 7.977 d 6.7 2.02 py 7.830 d 16.6 1.03 vinyl 7.624 d6.1 2.04 phe 7.110 d 16.9 1.00 vinyl 6.828 d 7.5 2.025 phe 4.233 s 3.03methyl 3.696 s 2.59 mms 3.637 t 6 2.1 ethylene 3.131 s 2.98 me am n2.728 t 6 2.0 ethylene

Example 6 Preparation of the Compound of Formula

One equivalent (14,0 g) of ethyl xanthogenate is dissolved with 75 mlabsolute ethanol in 20 g of the compound of formula (104a).

The temperature is raised to reflux and maintained at 80° C. during thefollowing 18 hours.

The product is crystallized by cooling to room temperature under mixing,than separated by filtration, washed and dried in the vacuum dryer.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz

8.493 d 6.7 1.98 py 7.929 d 6.7 2.02 py 7.772 d 16.6 1.03 vinyl 7.607 d6.1 2.04 phe 7.033 d 16.9 1.00 vinyl 6.812 d 7.5 2.025 phe 4.2294 s 3.03methyl 3.818 6 3.111 s 2.98 me am n 3.638 t 7 2.05 ethylene 2.75 t 72.00 ethylene

Example 7 Preparation of the Compound of Formula

One equivalent (9.0 g) of potassium thiocyanate is dissolved with 100 mlabsolute ethanol in 20 g of the compound of formula (104a).

The temperature is raised to reflux and maintained at 80° C. during thefollowing 36 hours.

The product is crystallized by cooling to room temperature under mixing,then separated by filtration, washed and dried in the vacuum dryer.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz

8.538 d 6.7 1.99 py 7.994 d 6.7 2.05 py 7.823 d 16.6 1.03 vinyl 7.645 d6.1 2.04 phe 7.119 d 16.9 1.03 vinyl 6.873 d 7.5 2.02 phe 4.2420 s 3.03methyl 3.882 t 6 1.87 ethylene 3.700 s 3.00 mms 3.28 T 7 2.09 ethylene3.137 s 2.98 me am n

Example 7 Preparation of the Compound of Formula

(a) Alkylation

2-methyl-pyridine (68.8 g) are dissolved in 80 ml absolute ethanol.

The temperature is raised to 333 K.

94 g dimethylsulfate are introduced in this mixture within one hour.

The temperature is maintained at 333 K during the following 3 h.

(b) Condensation

the equivalent amount (150 g) 2-chloroethyl-methylamino-benzaldehyde,250 ml ethanol and a catalitical amount (9,6 g) piperidine are added tothe reaction mixture obtained in step (a) and is stirred for 18 hours at343 K.

The reaction product is precipitated by cooling, then separated byfiltration and dried in vacuum to obtain 220 g of an orange solidproduct of formula

The product is recrystallized twice from methanol.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz

8.720 d 6.7 1.00 py 8.408 d 6.7 1.02 py 8.319 t 7 0.98 py 7.834 d 16.61.03 vinyl 7.679 t 7 1.02 py 7.576 d 7.1 2.04 phe 7.157 d 16.9 1.00vinyl 6.645 d 7.5 2.025 phe 4.268 s 3.03 methyl 3.818 t 6 2.00 ethylene3.748 t 6 2.05 ethylene 3.696 s 2.59 mms 3.152 s 2.98 me am n(c):

One equivalent (6,0 g) of thiourea is dissolved in the compound offormula (107a) with absolute ethanol.

The temperature is raised to reflux and maintained at 80° C. during thefollowing 48 hours.

(d) Hydrolysis

One equivalent (4.0 g) sodium hydroxide is dissolved to the substanceobtained in step (c) with absolute ethanol.

The temperature is maintained at 80° C. during the following 4 hours.

The product is crystallized by cooling to room temperature under mixing,than separated by filtration, washed and dried in the vacuum dryer.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz

8.720 d 6.7 1.00 py 8.408 d 6.7 1.02 py 8.319 t 7 0.98 py 7.834 d 16.61.03 vinyl 7.679 t 7 1.02 py 7.576 d 7.1 2.04 phe 7.157 d 16.9 1.00vinyl 6.645 d 7.5 2.025 phe 4.268 s 3.03 methyl 3.849 t 6 2.00 ethylene3.696 s 2.59 mms 3.280 t 6 2.11 ethylene 3.152 s 2.98 me am n

Example 8 Preparation of the Compound of Formula

(a) Alkylation

250 g of 4-methyl-quinoline are dissolved in 80 ml absolute ethanol.

The temperature was raised to 333 K.

94 g dimethylsulfate are introduced into this mixture within one hour.

The temperature is maintained at 333 K during the following 2.5 hours.

(b) Condensation

The equivalent amount (1500 g) of2-chloroethyl-methylamino-benzaldehyde, 250 ml ethanol and a catalyticalamount (9.6 g) of piperidine are added to the reaction mixture obtainedin step (a) and the reaction mixture stirred for 8 hours at,

The reaction product is precipitated by cooling, then separated byfiltration and dried in vacuum to obtain 340 g of an orange solidproduct of formula

The product is recrystallized twice from methanol.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz and shows a complex spectra. Through HPLC/MS theidentity was proofed, obtaining a single peak with the mass of 337/339dalton.

(c)

One equivalent (6.0 g) thiourea is dissolved in 30 g of the compound offormula (108a) with absolute ethanol.

The temperature is raised to reflux and maintained at 80° C. during thefollowing 48 hours.

The product is crystallized by cooling to room temperature under mixing,than separated by filtration, washed and dried in vacuum dryer.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz

Through HPLC/MS the identity was proofed, obtaining a single peak withthe mass of 377 dalton

Example 9 Preparation of the Compound of Formula

(a)

One equivalent (6.0 g) of thiourea is dissolved in 30 g of the compoundof formula (108a) with absolute. ethanol.

The temperature is raised to reflux and maintained at 80° C. during thefollowing 48 hours.

(b) Hydrolysis

One equivalent (4.0 g) sodium hydroxide is dissolved in the substanceobtained in step (a) with absolute ethanol.

The temperature is maintained at 80° C. during the following 4 hours.

The product is crystallized by cooling to room temperature under mixing,than separated by filtration, washed and dried in the vacuum dryer.

Through HPLC/MS the identity was proofed, obtaining a single peak withthe mass of 333 dalton

Example 10 Preparation of the Compound of Formula

(a) Alkylation

250 g 2-methyl-quinoline are dissolved in 80 ml absolute ethanol.

The temperature is raised to 333 K.

94 g dimethylsulfate are introduced within one hour into that mixture.

The temperature is maintained at 333 K during the following 2.5 hours.

(b) Condensation

The equivalent amount (150.0 g) of2-chloroethyl-methylamino-benzaldehyde, 250 ml ethanol and a catalyticalamount (9.6 g) of piperidine are added to the reaction mixture obtainedin step (a) and the reaction mixture stirred for 8 hours at,

The reaction product is precipitated by cooling, then separated byfiltration and dried in vacuum to obtain 340 g of an orange solidproduct of formula compound of formula (110).

The product is recrystallized twice from methanol.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz Showing a complex spectrum. Through HPLC/MS theidentity was proofed, obtaining a single peak with the mass of 337/339dalton

Example 11 Preparation of the Compound of Formula

One equivalent (6.0 g) thiourea is dissolved in 30 g of the compound offormula (110a) with absolute.

The temperature is raised to reflux and maintained at 80° C. during thefollowing 48 hours.

The product is crystallized by cooling to room temperature under mixing,than separated by filtration, washed and dried in vacuum dryer.

Through HPLC/MS the identity was proofed, obtaining a single peak withthe mass of 334 dalton

Example 12 Preparation of the Compound of Formula

(a) Alkylating Agent

A mixture of 15.4 g 2,2-dithiodiethanol in 100 ml chloroform and 24.1 gpyridine are cooled with stirring to 0° C. and then 41.0 g of tosylchloride are added in small amounts, maintaining the temperature.

After completion of the addition the mixture is left over night in therefrigerator and the reaction is finished.

The reaction mixture is mixed with a water/hydrochloric acid and iceslurry, the phases are separated, washed with water and dried.

The solution of toluenesulfonate diester is used for step (b).

(b) Alkylation

The alkylation agent obtained in step (a) is freed from the solvent anddissolved in two equivalent amounts of 2-methyl-pyridine.

The temperature is raised to 60° C. and maintained at 60° C. during thefollowing 24 hours.

(c) Condensation

50 ml dimethyl-formamide are added to the reaction mixture obtained instep (b).

The equivalent amount of 2-chloroethyl-methylamino-benzaldehyde and acatalytical amount of piperidine are added and the reaction mixture isstirred for 40 hours at 80° C.

The reaction product is precipitated by cooling, then separated byfiltration and dried in vacuum to obtain 39 g of an orange solidproduct.

The product is recrystallized twice from isopropanol.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz

9.62 d 6.8 1.00 py 828 t 6.7 0.98 py 7.92 d 6.7 1.02 py 7.81 t 6.6 1.03py 7.701 d 7.0 1.97 tosilate 7.58 d 6.1 1.967 phe 7.180 s 1.025 vinyl7.11 d 6.9 1.846 tosilate 6.71 d 6.4 2.05 phe 5.10 m 2.00 ethylene 3.56m 2.05 ethylene 3.818 t 6 2.05 ethylene 3.748 t 6 1.96 ethylene 3.04 s3.08 methyl(amine) 2.326 s 2.97 me-tosilate(d)

One equivalent (5,0 g) of thiourea is dissolved in 20 g of the foregoingalkylating dye with 75 ml absolute ethanol.

The temperature is raised to reflux and maintained at 80° C. during thefollowing 48 hours.

(e) Hydrolysis

One equivalent (4,0 g) of sodium hydroxide is dissolved with absoluteethanol as solvent in the substance of step (d).

The temperature was maintained at 80° C. during the following 4 hours.

The product is crystallized by cooling to room temperature under mixing,than separated by filtration, washed and dried in the vacuum dryer.

The product is characterized by ¹H-NMR data in deuterated chloroform(128 scans)/360 MHz

9.62 d 6.8 1.00 py 828 t 6.7 0.98 py 7.92 d 6.7 1.02 py 7.81 t 6.6 1.03py 7.701 d 7.0 1.97 tosilate 7.58 d 6.1 1.967 phe 7.180 s 1.025 vinyl7.11 d 6.9 1.846 tosilate 6.71 d 6.4 2.05 phe 5.10 m 2.00 ethylene 3.56m 2.05 ethylene 3.949 t 6 2.05 ethylene 3.280 t 6 1.96 ethylene 3.04 s3.08 methyl(amine) 2.326 s 2.97 me-tosilate

B. Applications Examples

The washing fastness of the dyed hair is analyzed by the Grey scaleaccording to Industrial organic pigments by Herbst&Hunger, 2nd ed. engl.S. 61) Nr 10: DIN 54 001-8-1982, “Herstellung und Bewertung derAenderung der Farbe”, ISO 105-A02-1993.

In the following application examples compositions within the belowgiven definitions are used:

Solution 1 (Permanent Lotion, pH 8.2):

Aqua, Ammonium Thioglycolate, Ammonium Bicarbonate, Ethoxydiglycol,Hexylene Glycol, Thioglycolic Acid; Thiolactic Acid, PEG-60 HydrogenatedCastor Oil, Glycine, Etidronic Acid, Isoceteth-20, Polysilicone-9,Styrene/PVP Copolymer, Trideceth-12, Amodimethicone, CetrimoniumChloride, Ammonium Hydroxide, Polyquaternium-6, Isopropyl Alcohol,Alcohol denat., Simethicone, Parfum

Solution 2 (Permanent Fixation, pH 3.9):

Based on:

Aqua, Hydrogen Peroxide, Propylene Glycol, Lauryldimonium HydroxypropylHydrolyzed Wheat Protein, PEG-5 Cocamide, Sodium Cocoamphoacetate,Polyquaternium-35, Coco-Betaine, Acetaminophen, Phosphoric Acid, SodiumChloride, Parfum

Solution 3 (Dyeing Solution):

0.1% of the dye is dissolved in a 10% solution of a non-ionic surfactant(Plantacare 200UP, Henkel) adjusted to pH 9.5 using citric acid ormonoethanolamine.

Example B1

50 mg of compound of formula (102d) according to example A1, isdissolved in 20 g ethanol and then 30 g of water is added: This reddyeing solution is applied on the dry hair (two blond, two middle blondand two damaged hair strands) and allowed to stand for 20 min. at roomtemperature. Then, the strands are rinsed under tap water and dried 12hours.

Washing fastness: 10× washed with shampoo.

Results: Strand Colour result Washing fastness blond Pink/good 2-3middelblond Pink/good 3-4 damaged Pink/good 3

Example B2

The 0.1%, by weight colouring material solution of example B1 is appliedon the dry hair (two blond, two middle blond, and two damaged hairstrands) and allowed to stand for 20 min. at room temperature. Then, thestrands are rinsed, and the towel dry strands are treated with thesolution 2 (permanent fixation) and allowed to stand for 10 min. Thenthe strands are rinsed under tap water and dried 12 hours at roomtemperature.

Washing fastness: 10× washed with shampoo.

Results: Strand Colour result Washing fastness blond Pink/good 2-3middelblond Pink/good 3-4 damaged Pink/good 3

Example B3

A solution 1 (permanent lotion) is applied on shampooed hair (two blond,two middle blond, and two damaged hair strands) and allowed to stand for10 min. Then, the strands are rinsed under tap water, and the towel drystrands are treated with the 0.1%, by weight colouring material solutionof example B1 allowed to stand for 20 min and then rinsed. Then, thetowel dry strands are treated with the solution 2 (permanent fixation)and allowed to stand for 10 min. Then the strands are rinsed under tapwater and dried 12 hours at room temperature.

Washing fastness: 10× washed with shampoo.

Results: Strand Colour Washing fastness blond Pink/good 3-4 middelblondPink/good 3-4 damaged Pink/good 3-4

1. Compounds of formula (1)

wherein R₁ is hydrogen; C₁-C₁₂alkyl; or phenyl-C₁-C₄alkyl; X isC₁-C₁₂alkylene; C₂-C₁₂alkenylene; C₅-C₁₀cycloalkylene; C₅-C₁₀arylene; orC₅-C₁₀arylene-C₁-C₁₀alkylene; Y is the residue of an organic dye whichcorresponds to the formula

wherein R₂ is hydrogen; or C₁-C₅alkyl; R₃ is a radical of formula

or R₂ and R₃ together with the linking carbon atom ¹C form a 6 to 10membered carbocyclic ring which may optionally be a condensated aromaticsystem and may contain one or more than one hetero atom; and R₄, R₅ andR₆ independently form each other are hydrogen, or C₁-C₅alkyl; Z is athio ester group of formula

wherein A is O; S; or N—R₉; B is —OR₇; —NR₇R₈; or —SR₇; and R₇, R₈ andR₉, independently from each other are hydrogen; C₁-C₁₂alkyl; C₆-C₁₂aryl;or C₆-C₁₂aryl-C₁-C₁₂alkyl.
 2. Compounds according to claim 1, wherein informula (1) X is C₁-C₁₂alkylene.
 3. Compounds according to claim 2,wherein X is ethylene.
 4. Compounds according to claim 1, wherein Y isselected from the radicals of formulae


5. Compounds according to claim 1, wherein Z is selected from theradicals of formulae

wherein R₇ and R₈ are defined as in claim
 1. 6. Compounds according toclaim 1, which correspond to formula

wherein R₁, R₃, X and Z are defined as in claim
 1. 7. A process for thepreparation of the compounds of formula (2), which comprisescondensating the active methylenic compound R₃H with the aminobenzaldehyde compound of formula (1c) to the compound of formula (1d)and subsequently alkylating this compound to give the compound offormula (2) according to the following reaction scheme:

wherein R₃ is radical of formula

and R₂ is simultaneously hydrogen; or R₂ and R₃ together with the linkedcarbon atom ¹C of formula (2) form a condensed carbocyclic ring offormula

Hal is a halogen atom; and R₁, X and Z are defined as in claim
 1. 8. Amethod of dyeing keratin-containing fibers comprising treating the fiberwith at least one dye of formula

wherein R₁ is hydrogen; C₁-C₁₂alkyl; or phenyl-C₁-C₄alkyl; X isC₁-C₁₂alkylene; C₂-C₁₂alkenylene; C₅-C₁₀cycloalkylene; C₅-C₁₀arylene; orC₅-C₁₀arylene-C₁-C₁₀alkylene; Y is the residue of an organic dye whichcorresponds to the formula

wherein R₂ is hydrogen; or C₁-C₅alkyl; R₃ is a radical of formula

R₂ and R₃ together with the linking carbon atom ¹C form a 6 to 10membered carbocyclic ring which may optionally be a condensated aromaticsystem and may contain one or more than one hetero atom; and R₄, R₅ andR₆ independently form each other are hydrogen, or C₁-C₅alkyl; Z is athio ester group of formula

wherein A is O; S; or N—R₉; B is —OR₇; —NR₇R₈; or —SR₇; and R₇, R₈ andR₉, independently from each other are hydrogen; C₁-C₁₂alkyl; C₆-C₁₂aryl;or C₆-C₁₂aryl-C₁-C₁₂alkyl.
 9. A method according to claim 8, wherein thedyeing is carried out in the absence of a reducing agent.
 10. A methodaccording to claim 8, wherein the dyeing is carried out in presence of areducing agent.
 11. A method according to claim 10, wherein the reducingagent is selected from the group consisting of thioglycol acid or saltsthereof, gycerine monothioglycolate, cystein, 2-mercaptopropionic acid,2-mercaptoethylamine, thiolactic acid, thioglycerine, sodium sulfite,dithionithe, ammonium sulfite, sodium bisulfite, sodium metabisulfiteand hydrochinon.
 12. A method according to claim 9, comprising treatingthe keratin-containing fiber (a) optionally with a reduction agent, and(b) at least one single dye of formula (1), and (c) optionally with anoxidizing agent.
 13. A composition comprising at least one dye offormula

wherein R₁ is hydrogen; C₁-C₁₂alkyl; or phenyl-C₁-C₄alkyl; X isC₁-C₁₂alkylene; C₂-C₁₂alkenylene; C₅-C₁₀cycloalkylene; C₅-C₁₀arylene; orC₅-C₁₀arylene-C₁-C₁₀alkylene; Y is the residue of an organic dye whichcorresponds to the formula

wherein R₂ is hydrogen; or C₁-C₅alkyl; R₃ is a radical of formula or

R₂ and R₃ together with the linking carbon atom ¹C form a 6 to 10membered carbocyclic ring which may optionally be a condensated aromaticsystem and may contain one or more than one hetero atom; and R₄, R₅ andR₆ independently form each other are hydrogen, or C₁-C₅alkyl; Z is athio ester group of formula

wherein A is O; S; or N—R₉; B is —OR₇; —NR₇R₈; or —SR₇; and R₇, R₈ andR₉, independently from each other are hydrogen; C₁-C₁₂alkyl; C₆-C₁₂aryl;or C₆-C₁₂aryl-C₁-C₁₂alkyl.
 14. A composition according to claim 13 inform of a shampoo, conditioner, gel or emulsion.
 15. A compositionaccording to claim 13 comprising at least one single dye of formula (1),and a direct dye and/or a reactive dye.